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Polyurethanes & Specialties
Polybenzoxazines : New ChemistryPolybenzoxazines : New Chemistry
Roger TietzeRoger Tietze
Robert KultzowRobert Kultzow
Tim TruongTim Truong
Huntsman Advanced Materials
PresentationPresentation
• IntroductionIntroduction• ChemistryChemistry• Material PropertiesMaterial Properties• Bisphenol A benzoxazineBisphenol A benzoxazine• ConclusionConclusion• Future DevelopmentsFuture Developments
Huntsman Advanced Materials
IntroductionIntroduction
Technology Origin:Technology Origin:
• Chemistry discovered in the 1930’sChemistry discovered in the 1930’s• Patent technology was acquired from a Swiss Patent technology was acquired from a Swiss
Research organization in the early 1990’sResearch organization in the early 1990’s• Huntsman has modified and enhanced the scope of Huntsman has modified and enhanced the scope of
benzoxazine technologybenzoxazine technology• Technology has been commercializedTechnology has been commercialized• Huntsman trade name : Azyrals Huntsman trade name : Azyrals
Huntsman Advanced Materials
ChemistryChemistry
• Benzoxazines are a unique non-halogen thermoset Benzoxazines are a unique non-halogen thermoset resin chemistryresin chemistry
• These compounds can be synthesized from phenols, These compounds can be synthesized from phenols, formaldehyde, and amines.formaldehyde, and amines.
• No halogen based precursorsNo halogen based precursors• Benzoxazines can homopolymerize to form a Benzoxazines can homopolymerize to form a
polybenzoxazine thermoset networkspolybenzoxazine thermoset networks• Benzoxazines also co-cure with epoxiesBenzoxazines also co-cure with epoxies• Electronics PWB market has a need for a non-Electronics PWB market has a need for a non-
halogen resin chemistry.halogen resin chemistry.
Huntsman Advanced Materials
Polybenzoxazine ChemistryPolybenzoxazine Chemistry
AdvantagesAdvantages• Potential low cost high performance thermosetPotential low cost high performance thermoset• High purity resin systemHigh purity resin system• High glass transition temperatureHigh glass transition temperature• Low shrinkageLow shrinkage• Low coefficient of thermal expansionLow coefficient of thermal expansion• Better moisture resistance.Better moisture resistance.• Better flammability resistance than epoxies and other Better flammability resistance than epoxies and other
thermosetsthermosets• Excellent electrical properties Excellent electrical properties
Huntsman Advanced Materials
Benzoxazine Synthesis
O H R3
R2
R1
H H
O N H 2 R4
N
O
R4
R3
R2
R1
-2H 2 O
2 x + +
Huntsman Advanced Materials
XU3560 Benzoxazine : XU3560 Benzoxazine : Bisphenol A benzoxazineBisphenol A benzoxazine
CH3
CH3
O O
NN
Huntsman Advanced Materials
Benzoxazine PolymerizationBenzoxazine Polymerization
N
OO
N
O
O
H
H
R1
R1
O
O
H
H
N
O
O
H
H
N
N N
R1
R1
Heat
Huntsman Advanced Materials
O
OR2
"O
O
N
OO
N
O
OO
R2"
O
O
OO
R2"
O
OH
R1
R1
O
O
H
N
OH
N
N N
R1
R1
OO
R2"
O
H H H
Catalyst
Heat
+
Epoxy
Benzoxazine/Epoxy PolymerizationBenzoxazine/Epoxy Polymerization
Huntsman Advanced Materials
Benzoxazine: Neat Resin Sample Preparation
To test the properties of benzoxazines and other thermosets, neat resin samples were prepared by the following procedure:
• Resins and hardeners are melted• Degassed• Poured into a mold• Cured with the appropriate cure cycle
Huntsman Advanced Materials
Neat Resin Castings
ResinResin TypeType CureCure
LZ8001LZ8001 FR4 bis A epoxyFR4 bis A epoxy 1 hour @ 177°C1 hour @ 177°C
MY720/DDSMY720/DDS High Tg epoxyHigh Tg epoxy 4 hour @ 200°C4 hour @ 200°C
Arocy B40Arocy B40 Cyanate EsterCyanate Ester 4 hours @ 218°C4 hours @ 218°C
BMI/DABABMI/DABA PolyimidePolyimide 4 hours @ 218°C4 hours @ 218°C
Polybenzoxazine APolybenzoxazine A BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C
Polybenzoxazine BPolybenzoxazine B BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C
Polybenzoxazine CPolybenzoxazine C BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C
Polybenzoxazine DPolybenzoxazine D BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C
Polybenzoxazine EPolybenzoxazine E BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C
Huntsman Advanced Materials
Neat Resin CastingsNeat Resin Castings
ResinResin Glass Transition Temperatures, °CGlass Transition Temperatures, °C
LZ8001 epoxy / DicyLZ8001 epoxy / Dicy 130°C – 140°C130°C – 140°C
MY720 / DDSMY720 / DDS 200°C200°C
Arocy B40Arocy B40 240°C240°C
BMI Resin/DABABMI Resin/DABA 240°C240°C
Polybenzoxazine APolybenzoxazine A 160°C160°C
Polybenzoxazine BPolybenzoxazine B 155°C155°C
Polybenzoxazine CPolybenzoxazine C 250°C250°C
Polybenzoxazine DPolybenzoxazine D 170°C170°C
Polybenzoxazine EPolybenzoxazine E 200°C200°C
• TMA Analysis
Huntsman Advanced Materials
UL94 Testing : Neat ResinUL94 Testing : Neat Resin
ResinResin 11stst Burn Burn 22ndndBurnBurn LengthLength RatingRating
LZ8001 / DicyLZ8001 / Dicy 8.08.0 N/aN/a Burn to clampBurn to clamp HBHB
MY720 / DDSMY720 / DDS 46.046.0 N/aN/a Burn to clampBurn to clamp HBHB
Arocy B40Arocy B40 15.615.6 7.87.8 3.23.2 V1V1
BMI Resin/DABABMI Resin/DABA 51.051.0 N/aN/a Burn to clampBurn to clamp HBHB
Polybenzoxazine APolybenzoxazine A 31.031.0 19.219.2 4.24.2 HBHB
Polybenzoxazine BPolybenzoxazine B 28.028.0 7.27.2 2.82.8 HBHB
Polybenzoxazine CPolybenzoxazine C 4.94.9 2.02.0 0.30.3 V0V0
Polybenzoxazine DPolybenzoxazine D 5.95.9 3.93.9 2.02.0 V1V1
Polybenzoxazine EPolybenzoxazine E 2.92.9 2.42.4 1.11.1 V0V0
Note: Longest burn time recorded
Huntsman Advanced Materials
Benzoxazine: Electrical TestingBenzoxazine: Electrical Testing
• Neat resin specimens : 0.5” x 0.5” Neat resin specimens : 0.5” x 0.5”
• Neat resin specimen thickness : 2.0 mm – 2.5 mmNeat resin specimen thickness : 2.0 mm – 2.5 mm
• HP4291A RF Impedance/Material AnalyzerHP4291A RF Impedance/Material Analyzer
• Linked to HP 16453A Dielectric Material Test Linked to HP 16453A Dielectric Material Test Fixture with a High Impedance Test HeadFixture with a High Impedance Test Head
• Calibration included the HP low loss capacitorCalibration included the HP low loss capacitor
• Frequency range : 1 MHz to 1.8 GHZFrequency range : 1 MHz to 1.8 GHZ
• Reported data range : 10 MHz – 1.5 GHZReported data range : 10 MHz – 1.5 GHZ
Huntsman Advanced Materials
Benzoxazine: Electrical Properties of Benzoxazine: Electrical Properties of Neat ResinsNeat Resins
Neat Resin SampleNeat Resin Sample DK RangeDK Range Df RangeDf Range
LZ8001LZ8001 3.5 – 3.73.5 – 3.7 0.020 – 0.0350.020 – 0.035
AER4100AER4100 3.5 – 3.73.5 – 3.7 0.020 – 0.0350.020 – 0.035
Arocy B40Arocy B40 2.80 – 2.972.80 – 2.97 0.0050 – 0.00900.0050 – 0.0090
Polybenzoxazine APolybenzoxazine A 3.00 – 3.153.00 – 3.15 0.0060 – 0.01000.0060 – 0.0100
Polybenzoxazine BPolybenzoxazine B 3.15 – 3.303.15 – 3.30 0.0070 –0.01100.0070 –0.0110
Polybenzoxazine CPolybenzoxazine C 3.45 – 3.603.45 – 3.60 0.0070 – 0.00900.0070 – 0.0090
Polybenzoxazine DPolybenzoxazine D 3.40 – 3.453.40 – 3.45 0.0065 – 0.00850.0065 – 0.0085
Frequency = 10 MHZ – 1.5 GHz
Huntsman Advanced Materials
• Benzoxazines more flame resistant than epoxiesBenzoxazines more flame resistant than epoxies• Good electrical propertiesGood electrical properties• High glass transition temperaturesHigh glass transition temperatures
Neat Resin ResultsNeat Resin Results
Huntsman Advanced Materials
Typical PropertiesTypical Properties XU3560XU3560
• Visual appearanceVisual appearance Yellow chunks Yellow chunks • Melting point, °CMelting point, °C 80-8580-85• Viscosity @ 125Viscosity @ 125C, cps C, cps 185185• Volatile, %Volatile, % ~2~2
DSC uncuredDSC uncured• Initiation Temperature To, Initiation Temperature To, CC 231231• Peak Temperature Tg, Peak Temperature Tg, CC 241241 H, J/gH, J/g 238238
Huntsman Advanced Materials
Mechanical PropertiesMechanical Properties
XU3560 Curing Cycle 2hr/180C + 2hr/200C Tg(C) DSC 171 Tg(C) DMA 163 Tg(C)DMA Wet* 150 Flex Properties Dry @ RT Modulus, ksi, (MPa) 667 (4602) Strength, ksi, (MPa) 19.1 (132) Tensile Properties Dry @ RT Modulus, ksi, (MPa) 773 (5334) Strength, ksi, (MPa) 4.5 (31) Elongation, % 1.2 Compression Properties Dry @ RT Modulus, ksi, (MPa) 508 (3505) Strength, ksi, (MPa) 33 (228) Elongation, % 8.3 Toughness Properties Dry @ RT KIc, lbin/in2, (MPam) 844 (0.94) GIc, in-lb/in2, (J/m2) 0.96 (168)
*48hrs boiling water
Huntsman Advanced Materials
Formulations for XU3560Formulations for XU3560
1 2 3
97-191 75 70 70 CY 179 25 30 30 Hycar CTBN1300x13 --- 10 XB 6079 3.50 3.50 Benzopinacol 1.05 1.05 Curing Cycle 2hr/180C +
2hr/200C 1hr/120C + 4hr/180C
1hr/120C + 4hr/180C
Tg(C) DSC 219 204 NT Tg(C) DMA, E’ 227 198 200 Tg(C)DMA, E’ Wet* 181 164 158 Flex Properties Dry @ RT Modulus, ksi, (MPa) 642 742 527 Strength, ksi, (MPa) 16.7 19.3 19.2 Tensile Properties Dry @ RT Modulus, ksi, (MPa) 626 722 564 Strength, ksi, (MPa) 7.6 7.4 12.6 Elongation, % 1.6 1.0 2.8 Toughness Properties Dry @ RT KIc, lbin/in2, (MPam) 581 NT 850 GIc, in-lb/in2, (J/m2) 0.47 NT 1.23
Huntsman Advanced Materials
Novel High Performance SystemsNovel High Performance Systems
Conclusions :Conclusions :
• We have developed unique benzoxazine resins with commercially We have developed unique benzoxazine resins with commercially
viable manufacturing processes. viable manufacturing processes.
• These resins afford wide formulation latitude and can be These resins afford wide formulation latitude and can be
formulated with epoxies, thermoplastics and catalysts to suit formulated with epoxies, thermoplastics and catalysts to suit
various applications and fabrication processes. various applications and fabrication processes.
• These resins are ideal for high performance composite, structural These resins are ideal for high performance composite, structural
adhesive and printing wiring board (PWB) applications. adhesive and printing wiring board (PWB) applications.
• The benzoxazine/epoxy systems have high TgThe benzoxazine/epoxy systems have high Tg°C°C, good thermal , good thermal
oxidation stability, low water pick-up, reduced shrinkage, good oxidation stability, low water pick-up, reduced shrinkage, good
electrical, and are room temperature stable. electrical, and are room temperature stable.
Huntsman Advanced Materials
Benzoxazine TechnologyBenzoxazine Technology
Current StatusCurrent Status• Technology development work continuesTechnology development work continues• New candidate products have been introduced for New candidate products have been introduced for
– Aerospace composite marketsAerospace composite markets– High performance laminating marketsHigh performance laminating markets
• We have cooperative developments programs with Key We have cooperative developments programs with Key customerscustomers
• Qualifications in progress at major customers in both Electronic Qualifications in progress at major customers in both Electronic and Aerospace segmentsand Aerospace segments
• Industrial applications are being exploredIndustrial applications are being explored• Manufacturing in place in North America and Europe.Manufacturing in place in North America and Europe.• Process development work to install manufacturing capability in Process development work to install manufacturing capability in
Asia in the near future.Asia in the near future.
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